Stereospecific ligands and their complexes. V. Synthesis, characterization and antimicrobial activity of palladium(II) complexes with some alkyl esters of (S,S)-ethylenediamine-N,N′-di-2-propanoic acid

Three new ligands and their palladium(II) complexes of general formula [PdCl₂(R₂-S,S-eddp)] (R = n-propyl, n-butyl and n-pentyl) have been synthesized and characterized by microanalysis, infrared and ¹H and ¹³C NMR spectroscopy. Antimicrobial activity of these ligands and complexes was tested by microdilution method and both minimal inhibitory and microbicidal concentration were determined. These tested complexes demonstrated the significant antifungal activity against pathogenic fungi Aspergillus flavus and Aspergillus fumigatus. On the other hand, these complexes demonstrated moderate antibacterial activity.     

The metabolism of urethane and related compounds

1. Urethane is metabolized in the rat, rabbit and man by a process of N-hydroxylation. This occurs to a smaller extent when methyl, n-propyl and n-butyl carbamates are administered to the rat and rabbit. 2. Other metabolites which have been detected in urine of animals dosed with urethane and N-hydroxyurethane are ethylmercapturic acid, ethylmercapturic acid sulphoxide and N-acetyl-S-carbethoxycysteine. 3. Substances which appear to be S-ethylglutathione and S-ethylglutathione sulphoxide have been detected in the bile of rats dosed with urethane or N-hydroxyurethane. 4. Methyl, ethyl, n-propyl and n-butyl N-hydroxycarbamates are excreted unchanged in the urine of rats dosed with these compounds to extents depending on the dose administered. 5. Animals dosed with methyl, ethyl, n-propyl or n-butyl carbamate or the corresponding N-hydroxycarbamate excrete the corresponding carbamate and N-hydroxycarbamate in the urine. 6. Methyl, n-propyl and n-butyl carbamates and N-hydroxycarbamates are excreted more slowly than are urethane and N-hydroxyurethane. 7. The probable role of N-hydroxyurethane and the processes of alkylation and carbethoxylation, and of hydroxylamine, nitroxyl and hyponitrous acid in carcinogenesis and chemotherapy with urethane, have been discussed.     

Neolignans from Aniba lancifolia

The branches of the shrub Aniba lancifolia Kubitzki et Rodrigues (Lauraceae) contain besides 2-hydroxy-4,5- dimethoxyallylbenzene and its dimer cyclohexan-2-allyl- 5-en-4,5-dimethoxy-4-O-(2′-allyl-4′,5′-dimethoxyphenyl)-1-one (lancilin, 2) 6 further novel neolignans: (4S,2′R)- and (4R,2′E)-cyclohexan-2-allyl-2,5-dien-4,5-dimethoxy-4-[2′-(1′-guaiacyl)-propyl]-1-one (lancifolins A and B, 3a and 3b), (4S,2′R)- and (4R,2′R)-cyclohexan- 2-allyl-2,5-dien-4,5-dimethoxy-4-[2′-(1′-veratryl)-propyl]-1-one (lancifolins C and D, 3c and 3d), (4S,2′R)-and (4R,2′R)-cyclohexan-2-allyl-2,5-dien-4,5-dimethoxy-4-[2′-(1′-piperonyl)-propyl]-1-one (lancifolins E and F, 3e and 3f).     

Preparation, properties and crystal structure of two isomers of R,R,S,S- and R,S,R,S-[chloro(1,3,10,12,16,19-hexaazatetracyclo[17,3,1,1,0]tetracosane)copper(II)]

Two isomers (R,S,R,S- and R,R,S,S-) of five coordinate complex [Cu(L)Cl]⁺ have been separated and characterised. These two isomers have significantly different spectrochemical and electrochemical properties. Absorption maximum of R,S,R,S-[Cu(L)Cl]⁺ shifts to longer wavelength and its reduction potential shifts to more positive direction comparing those of R,R,S,S-[Cu(L)Cl]⁺. R,S,R,S-[Cu(L)Cl]⁺ is significantly distorted to trigonal-bipyramidal structure, whereas R,R,S,S-[Cu(L)Cl]⁺ retains almost square-planar geometry. The average bond distance of Cu-N in basal plane of R,S,R,S-[Cu(L)Cl]⁺ is longer by 0.024 Å than that of R,R,S,S-[Cu(L)Cl]⁺, whereas the bond distance of Cu-Cl in former is shorter by 0.200 Å than that in latter. The isolated square-planar complexes of R,R,S,S- and R,S,R,S-[Cu(L)](ClO₄)₂ are converted to the R,R,S,S- and R,S,R,S-[Cu(L)Cl]⁺ by the addition of Cl⁻ in nitromethane solution with the rate constants, k=1.70 (±0.02) and 8.31 (±0.07) M⁻¹ s⁻¹, respectively.     

Repellent activity of catmint, Nepeta cataria, and iridoid nepetalactone isomers against Afro-tropical mosquitoes, ixodid ticks and red poultry mites

The repellent activity of the essential oil of the catmint plant, Nepeta cataria (Lamiaceae), and the main iridoid compounds (4aS,7S,7aR) and (4aS,7S,7aS)-nepetalactone, was assessed against (i) major Afro-tropical pathogen vector mosquitoes, i.e. the malaria mosquito, Anopheles gambiae s.s. and the Southern house mosquito, Culex quinquefasciatus, using a World Health Organisation (WHO)-approved topical application bioassay (ii) the brown ear tick, Rhipicephalus appendiculatus, using a climbing repellency assay, and (iii) the red poultry mite, Dermanyssus gallinae, using field trapping experiments. Gas chromatography (GC) and coupled GC-mass spectrometry (GC-MS) analysis of two N. cataria chemotypes (A and B) used in the repellency assays showed that (4aS,7S,7aR) and (4aS,7S,7aS)-nepetalactone were present in different proportions, with one of the oils (from chemotype A) being dominated by the (4aS,7S,7aR) isomer (91.95% by GC), and the other oil (from chemotype B) containing the two (4aS,7S,7aR) and (4aS,7S,7aS) isomers in 16.98% and 69.83% (by GC), respectively. The sesquiterpene hydrocarbon (E)-(1R,9S)-caryophyllene was identified as the only other major component in the oils (8.05% and 13.19% by GC, respectively). Using the topical application bioassay, the oils showed high repellent activity (chemotype A RD₅₀ = 0.081 mg cm⁻² and chemotype B RD₅₀ = 0.091 mg cm⁻²) for An. gambiae comparable with the synthetic repellent DEET (RD₅₀ = 0.12 mg cm⁻²), whilst for Cx. quinquefasciatus, lower repellent activity was recorded (chemotype A RD₅₀ = 0.34 mg cm⁻² and chemotype B RD₅₀ = 0.074 mg cm⁻²). Further repellency testing against An. gambiae using the purified (4aS,7S,7aR) and (4aS,7S,7aS)-nepetalactone isomers revealed overall lower repellent activity, compared to the chemotype A and B oils. Testing of binary mixtures of the (4aS,7S,7aR) and (4aS,7S,7aS) isomers across a range of ratios, but all at the same overall dose (0.1 mg), revealed not only a synergistic effect between the two, but also a surprising ratio-dependent effect, with lower activity for the pure isomers and equivalent or near-equivalent mixtures, but higher activity for non-equivalent ratios. Furthermore, a binary mixture of (4aS,7S,7aR) and (4aS,7S,7aS) isomers, in a ratio equivalent to that found in chemotype B oil, was less repellent than the oil itself, when tested at two doses equivalent to 0.1 and 0.01 mg chemotype B oil. The three-component blend including (E)-(1R,9S)-caryophyllene at the level found in chemotype B oil had the same activity as chemotype B oil. In a tick climbing repellency assay using R. appendiculatus, the oils showed high repellent activity comparable with data for other repellent essential oils (chemotype A RD₅₀ = 0.005 mg and chemotype B RD₅₀ = 0.0012 mg). In field trapping assays with D. gallinae, addition of the chemotype A and B oils, and a combination of the two, to traps pre-conditioned with D. gallinae, all resulted in a significant reduction of D. gallinae trap capture. In summary, these data suggest that although the nepetalactone isomers have the potential to be used in human and livestock protection against major pathogen vectors, intact, i.e. unfractionated, Nepeta spp. oils offer potentially greater protection, due to the presence of both nepetalactone isomers and other components such as (E)-(1R,9S)-caryophyllene.     

Selection for increased vernolate tolerance in tobacco (Nicotiana tabacum L.) cell cultures

Vernolate (S-propyl N, N-dipropylthiocarbamate) has been used to select thiocarbamate-tolerant tobacco cell lines. Cross-tolerance to other thiocarbamate herbicides was observed. Tolerance was initially unstable in the absence of continued selection, but shoot regeneration produced plants in which some tolerance was stably expressed. Morphological abnormalities in the regenerated plants are described.     

Survival,prophage induction,and invasive properties of lysogenic Salmonella Typhimurium exposed to simulated gastrointestinal conditions

This study was designed to evaluate the viability, prophage induction, invasive ability, and relative gene expression in lysogenic Salmonella Typhimurium exposed to the simulated gastric juice (SGJ) at pH 2 (SGJ-2), 3 (SGJ-3), 4 (SGJ-4), and 5 (SGJ-5) for 30 min followed by 0.5 % bile salts for 2 h. The susceptibility of lysogenic S. Typhimurium increased with decreasing pH value and increasing bile salt concentration. The lysogenic S. Typhimurium cells were least susceptible to SGJ-4 and SGJ-5, showing <1 log reduction. The highest prophage induction was observed by 3.34 log PFU/ml in lysogenic S. Typhimurium at SGJ-3 in the presence of 0.5 % bile salts. The numbers of invading lysogenic S. Typhimurium treated at SGJ-3, SGJ-4, and SGJ-5 were 3.57, 3.73, and 4.15 log CFU/cm², respectively. Most genes (hilA, hilC, hilD, invA, invE, invF, and sirA) were down-regulated in lysogenic S. Typhimurium treated at SGJ-3, SGJ-4, and SGJ-5. This study provides useful information for understanding physiological changes of lysogenic S. Typhimurium in the simulated gastrointestinal conditions.     

Chiral inorganic [16O, 17O, 18O]thiophosphate: Synthesis and stereochemical analysis

(S)-2-Iodo-1-phenylethanol has been synthesized and shown to be a reagent for the stereochemical analysis of chiral inorganic [¹⁶O, ¹⁷O, ¹⁸O]thiophosphate. R and S Inorganic ¹⁶O, ¹⁷O, ¹⁸O-labeled thiophosphates were synthesized and treated with the iodo compound to give chirally labeled 1(S)-phenylethanol-2-S-thiophosphate, which after cyclization with diphenylphosphoryl chloride followed by methylation with diazomethane could be distinguished by ³¹P NMR spectroscopy. The cyclization step was shown to proceed with inversion of configuration at phosphorus.     

Improvement of carbonyl reductase activity for the bioproduction of tert-butyl (3R,5S)-6-chloro-3,5-dihydroxyhexanoate

tert-Butyl (3R,5S)-6-chloro-3,5-dihydroxyhexanoate ((3R,5S)-CDHH) is a key chiral intermediate for the side chain synthesis of rosuvastatin. In this study, random mutagenesis, site-saturation mutagenesis and combinatorial mutagenesis methods were applied to improve the activity of a synthesized stereoselective short chain carbonyl reductase (SCR) to prepare (3R,5S)-CDHH. After screened by high-throughput screening method and high-performance liquid chromatography, mut-Phe145Met/Thr152Ser and mut-Phe145Tyr/Thr152Ser, were obtained, and the enzyme activities of mutants were improved by 1.60- and 1.91-fold compared with parent enzyme, respectively. The catalytically efficiencies (kcat/Km) of mut-Phe145Met/Thr152Ser and mut-Phe145Tyr/Thr152Ser exhibited 5.11- and 8.07-fold improvements in initial activity toward (S)-6-chloro-5-hydroxy-3-oxohexanoate ((S)-CHOH), respectively. In the asymmetric reduction, mut-Phe145Tyr/Thr152Ser catalyzed 500 g L⁻¹ of (S)-CHOH to produce (3R,5S)-CDHH with >99% yield and >99% e.e., and the highest space-time yield achieved at 752.76 mmol L⁻¹ h⁻¹ g⁻¹ wet cell weight within 8 h bioconversion. This study provides a foundation for the preparation of (3R,5S)-CDHH by carbonyl reductase.     

On the Molecular Characterization of the Sodium-Potassium Transport Adenosine Triphosphatase

The phosphorylated intermediate in the (Na + K)-activated adenosine triphosphatase (Na-K ATPase) has been characterized as an L-glutamyl-γ-phosphate residue in the enzyme. This has been accomplished by digestion of the phosphorylated and nonphosphorylated forms of the enzyme with pepsin, reaction of the pepsin digests with [2,3-³H]N-(n-propyl)hydroxylmine, further digestion of the derivatized peptides with pronase in the presence of carrier L-glutamyl-γ-N-(n-propyl)hydroxamate and carrier L-aspartyl-N-(n-propyl)hydroxamate, and chromatographic purification. An increment in radioactivity migrated with authentic L-glutamyl-γ-N-(n-propyl)hydroxamate in a total of seven electrophoretic and chromatographic systems and on gel filtration. No increment in radioactivity was associated with authentic L-aspartyl-β-N-(n-propyl)hydroxamate in five out of the seven chromatographic and electrophoretic systems. At the last stage of purification the radioactivity from the phosphorylated enzyme which migrated as L-glutamyl-γ-N-(n-propyl)hydroxamate was 2½ times that from the nonphosphorylated enzyme. On the basis of these results it is concluded that the phosphorylated intermediate in the Na-K ATPase is an L-glutamyl-γ-phosphate residue. The beef brain Na-K ATPase has been solubilized with the nonionic detergent, Lubrol, and has been purified 10 times over that in the original microsomes. The soluble enzyme remains stable in the presence of ATP and either Na⁺ or K⁺. If the partially purified enzyme is electrophoresed in 3% polyacrylamide, followed by incubation with ATP, Na⁺, K⁺, and Mg⁺⁺, a single, somewhat diffuse, ATPase band, which is ouabain-sensitive is seen. Protein impurities are also seen on the gel. Gel electrophoresis, after treatment of the partially purified enzyme with phenol-acetic acid-urea, shows about 12 discrete protein bands. Studies on the site-directed alkylation of the (Na + K)-activated adenosine triphosphatase with haloacetate derivatives of cardiotonic steroids are reviewed. Efforts are now underway to specifically alkylate the cardiotonic steroid site of the Na-K ATPase with hellebrigenin 3-[2-³H]iodoacetate and to purify the subunit of the enzyme containing the cardiotonic steroid site by following radioactivity. Finally, a working model for the role of the Na-K ATPase in the coupled transport of Na and K is presented.     

An active site-directed, irreversible inactivation of yeast hexokinase by (R,S)2,3-epoxypropyl beta-D-glucopyranoside

(1) Only (R,S)2′,3′-epoxypropyl β-d-glucopyranoside of the complete series of mono (R,S)2′.3′-epoxypropyl ethers and glycosides of d-glucopyranose significantly inactivated yeast hexokinase.(2) (R,S)2′,3′-Epoxypropyl β-d-glucopyranoside inactivates yeast hexokinase in the absence of MgATP^2?, The rate of inactivation is unaffected by MgATP^2?.(3) The rate of inactivation of hexokinase with (R,S)2′,3′-epoxypropyl β-d-ilucopyranoside was much greater when hexokinase was present in a monomeric form than when it was present in a dimeric form.(4) (R,S)2′,3′-Epoxypropyl β-d-glucopyranoside has a high K_t (0.38 M) and at a saturating concentrarion, the first order rate constant for the inactivation of monomeric hexokinase is 8.3 · 10^?4 sec.(5) d-Glucose protects against this inactivation and this was used to derive a dissocistion constant of 0.21 mM for d-glucose in the absence of MgATP^2?.(6) The alkylation of yeast hexokinase by (R,S)2′,3′-epoxypropyl β-d-gluco-pyranoside was not specific to the active site. When the concentration of (R,S)2′,3′-epoxypropyl β-d-glucopyranoside was 50 mM two thiol groups outside the active site were also alkylated.(7) The reaction between 5,5′-dithiobis-(2-nitrobenzoic acid) (DTNB) and yeast hexokinase was examined in detail. Two thiol groups per monomer (mol. wt. 50000) reacted with a second order rate constant of 27 1 mole^?1 sec^?1. A third thiol group reacted more slowly with a second-order rate constant of 1.6 1 mole^?1 sec^?1 and a fourth thiol group reacted very slowly with inactivation of the enzyme. Tue second-order rate constant in this case was 0.1 1 mole^?1 sec^?1.     

The S-n-propyl analogue of S-adenosylmethionine

A special strain of Saccharomyces cerevisiae responded to a supplement of S-n-propyl-l-homocysteine in the culture medium by synthesizing S-adenosyl-(S-n-propyl)l-homycysteine, the S-n-propyl analogue of S-adenosylmethionine. S-n-Butyl-l-homocysteine reacted sparingly with this strain, but S-isopropyl-l-homocysteine failed to form detectable quantities of the corresponding S-adenosylsulfonium were compound. The S-n-propyl compound was isolated by extraction of the cells, followed by ion-exchange chromatography, which separated it from endogenous S-adenosylmethionine. The structure was determined by hydrolytic procedures leading to overlapping fragments of known structure, 5′-n-propylthioadenosine and S-n-propyl-l-homocysteine. The new sulfonium compound was examined for its activity as n-propyl donor by substituting it for S-adenosylmethionine in methyltransferase systems. Enzymatic transpropylation was observed with S-adenosylmethionine: l-homocysteine S-methyltransferase (EC 2.1.1.10). Its rate was low in the S-adenosylmethionine: N-acetylserotonin O-methyltransferase system (EC 2.1.1.4), and below recognition with S-adenosylmethionine: guanidonoacetate methyltransferase (EC 21.1.2) and S-adnosylmethionine: histame N-methyltransferase (EC 2.1.1.8).     

Apple S locus region represents a large cluster of related, polymorphic and pollen-specific F-box genes

Gametophytic self-incompatibility (GSI) of Rosaceae, Solanaceae and Plantaginaceae is controlled by a complex S locus that encodes separate proteins for pistil and pollen specificities, extracellular ribonucleases (S-RNases) and F-box proteins SFB/SLF, respectively. SFB/SLFs of Prunus (subfamily Prunoideae of Rosaceae), Solanaceae and Plantaginaceae are single copy in each S haplotype, while recently identified pollen S candidates SFBBs of subfamily Maloideae of Rosaceae, apple and Japanese pear, are multiple; two and three related SFBBs were isolated from each S haplotype of apple and Japanese pear, respectively. Here, we show that apple (Malus × domestica) SFBBs constitute a gene family that is much larger than initially thought. Twenty additional SFBB-like genes/alleles were isolated by screening of a BAC library derived from S ³ S ⁹ genotype, and tentatively named MdFBX1-20. All but one MdFBX showed S haplotype-specific polymorphisms. All the polymorphic MdFBXs were completely linked to S-RNase in 239 segregants. In addition, FISH revealed that the monomorphic gene MdFBX11 is also located near S-RNase, and the S locus is located in a subtelomeric region of a chromosome and is not close to the centromere. All MdFBXs were specifically expressed in pollen, except for a pseudogene MdFBX4 that showed no expression in any organs analyzed. Phylogenetic analysis revealed that the closest relatives of most MdFBXs were from a different S haplotype, suggesting that proliferation of MdSFBB/FBXs predates diversification of the S haplotypes.     

Effects of Spartina alterniflora Invasion on Soil Respiration in the Yangtze River Estuary,China

Many studies have found that plant invasion can enhance soil organic carbon (SOC) pools, by increasing net primary production (NPP) and/or decreased soil respiration. While most studies have focused on C input, little attention has been paid to plant invasion effects on soil respiration, especially in wetland ecosystems. Our study examined the effects of Spartina alterniflora invasion on soil respiration and C dynamics in the Yangtze River estuary. The estuary was originally occupied by two native plant species: Phragmites australis in the high tide zone and Scirpus mariqueter in the low tide zone. Mean soil respiration rates were 185.8 and 142.3 mg CO₂ m⁻² h⁻¹ in S. alterniflora and P. australis stands in the high tide zone, and 159.7 and 112.0 mg CO₂ m⁻² h⁻¹ in S. alterniflora and S. mariqueter stands in the low tide zone, respectively. Aboveground NPP (ANPP), SOC, and microbial biomass were also significantly higher in the S. alterniflora stands than in the two native plant stands. S. alterniflora invasion did not significantly change soil inorganic carbon or pH. Our results indicated that enhanced ANPP by S. alterniflora exceeded invasion-induced C loss through soil respiration. This suggests that S. alterniflora invasion into the Yangtze River estuary could strengthen the net C sink of wetlands in the context of global climate change.     

Synthesis of (R,S)-isoproterenol,an inhibitor of tau aggregation,as an 11C-labeled PET tracer via reductive alkylation of (R,S)-norepinephrine with [2-11C]acetone

(R,S)-Isoproterenol inhibits the formation of toxic granular tau oligomers associated with neuronal loss and development of cognitive disorders, and is an attractive drug candidate for Alzheimer’s disease. To elucidate its behavior in the brain by positron emission tomography, we synthesize (R,S)-[¹¹C]isoproterenol by reductive alkylation of (R,S)-norepinephrine with [2-¹¹C]acetone, which was in turn synthesized in situ under improved conditions afforded a decay-corrected radiochemical yield of 54%. The reductive alkylation using NaBH(OAc)₃ as reducing agent in the presence of benzoic acid in DMSO/DMF (60:40 v/v) at 100 °C for 10 min gave (R,S)-[¹¹C]isoproterenol in an 87% radio-high performance liquid chromatography (HPLC) analytical yield. HPLC separation using a strong cation exchange column, followed by pharmaceutical formulation in the presence of d/l-tartaric acid, afforded (R,S)-[¹¹C]isoproterenol with a total radioactivity of 2.0 ± 0.2 GBq, a decay-corrected radiochemical yield of 19 ± 2%, chemical and radiochemical purities of 71% and >99%, respectively, and a molar activity of 100 ± 13 GBq/μmol (n = 3). The overall synthesis time from the end of the bombardment to pharmaceutical formulation was 48 min. A preliminary preclinical PET study in a rat demonstrated the potential of the radioligand for the evaluation of the penetration of (R,S)-isoproterenol in human brain.     

Characterization of bio-related vanadium and zinc complexes containing tetradentate dithiolate-disulfide, -diamine and -amine-amide ligands

The reaction of [VCl₃(PMe₂Ph)₃] _{with HSS′S′SH (where the HS are thiophenolate and the S′ thioether functions, respectively), H2–1, yields [VCl(μ-SS′S′S)]2 (3) with one of the thiolate groups of each of the two ligands in the bridging mode. Reaction of Na2–1 with [VOCl2(thf)2] leads to a polymeric product of composition [VO(SS′S′S)]x (4). The products obtained from the reaction between [VOCl2(thf)2] and NaSNNSNa, Na2–2, (S is thiophenolate, N the amine function) depend on subtle changes in the diamine backbone of this ligand: If the amine functions are linked by -CH2CH2– (2a), the tetranuclear V^IV complex [V(SNNS)μ-O]4 (5) is formed alongside the V^III complex [VCl(SNNS)]. If the backbone is -CH(Me)CH(Me)- (2b), [VO(SNNS)] (7) and the dinuclear, asymmetrically oxo-bridged V^IV complex [{(SNN ^– S)(thf)V}μ-O{V(SNN ^– S)}] (8) are obtained. In 8, one amine of each of the two ligands is deprotonated to the amide group. In either case, the complexation is accompanied by oxidation of the thiolates to disulfides, leading to the generation of teraazatetrathio-cycloeicosanes (6a/b). Compounds 5 and 8·2THF have been structurally characterized by X-ray analyses. The connectivities have further been established for 3·2CH2Cl2 and for 6b, which exhibits the same conformation as formally characterized 6a. The cluster compound 5 is stabilized by an extended intramolecular N-H...O and N-H...S) hydrogen-bonding network. In 7·2THF, one of the THFs of crystallization is hydrogen-bonded to the NH of the penta-coordinated {VO(SNN ^– S)} moiety; further, there is an intramolecular hydrogen bond between one of the thiolates of this tetragonal-pyramidal half of the molecule and the NH of the octahedral {VO(SNN ^– S)thf} half. The generation of the ligand 2b from its precursor compound, the zinc complex [Zn(SNNS)] (9) leads to the structural characterization of 9·CH3OH with a large SZnS bite angle and a strong hydrogen bond between the methanolic OH and one of the thiolate sulfurs. The relevance of these compounds in biological systems is discussed.}     

Sulcatine,a norsesquiterpene from the fungus Laurilia sulcata

The structure of sulcatine, a novel protoilludene norsesquiterpene isolated from a culture of Laurilia sulcata, has been assigned on the basis of a detailed study of its ¹H NMR and ¹³C NMR spectra and chemical evidence. The relative configuration was deduced from the observed ¹H {¹H} nuclear Overhauser effects (NOEs) and from the values of ¹H¹H coupling constants. The application of the exciton chirality method on the dibenzoate permitted establishment of the absolute configuration of sulcatine as 2S,3R,7S,8S,9R.     

Synthesis of (R)- or (S)-valinol using ω-transaminases in aqueous and organic media

Valinol is part of numerous pharmaceuticals and has various other important applications. Optically pure valinol (ee >99%) was prepared employing different ω-transaminases from the corresponding prochiral hydroxy ketone. By the choice of the enzyme the (R)- as well as the (S)-enantiomer were accessible. Reductive amination was performed in organic solvent (MTBE) using 2-propyl amine as amine donor whereas alanine was applied in or in aqueous medium. Transformations in phosphate buffer were successfully performed even at 200 mM substrate concentration (20.4 g/L) leading to 99% (R) and 94% (S) conversion with perfect optical purity (>99% ee).     

Electrochemical behavior of S,S-bridged adducts of square planar metalladithiolene complexes [M(S2C2Ph2)2](M=Ni, Pd, and Pt)

The electrochemical behavior of the S,S^′-bridged adducts of square planar metalladithiolene complexes was investigated by using cyclic voltammetry and electrochemical spectroscopies (visible, near-IR, and ESR). The norbornene-bridged S,S^′-adduct [Ni(S₂C₂Ph₂)₂(C₇H₈)] (2a; C₇H₈=norbornene) formed by [Ni(S₂C₂Ph₂)₂] (1a) and quadricyclane (Q) was dissociated by an electrochemical reduction, and anion 1a⁻ and norbornadiene (NBD) were formed. Q was isomerized to NBD in the overall reaction. The o-xylyl-bridged S,S^′-adduct [Ni(S₂C₂Ph₂)₂(CH₂)₂(C₆H₄)] (3a; (CH₂)₂(C₆H₄)=o-xylyl) was also dissociated by an electrochemical reduction, and this reaction gave the o-xylyl radical (o-quinodimethane). The reduction of complex 3a in the presence of excess o-xylylene dibromide underwent the catalytic formation of o-quinodimethane. The butylene-bridged S,S^′-adduct [Ni(S₂C₂Ph₂)₂(CH₂)₄] (4a; (CH₂)₄=butylene) was stable on an electrochemical reduction. The lifetimes of reduced species of these adducts 2a-4a were influenced by the stability of the eliminated group (stability: NBD > o-xylyl radical (o-quinodimethane) > butylene radical). Therefore, the reduced species are stable in the sequence 4a⁻ > 3a⁻ > 2a⁻. Although the palladium complex [Pd(S₂C₂Ph₂)₂] (1b) was easier to reduce than the nickel complex 1a or the platinum complex [Pt(S₂C₂Ph₂)₂] (1c), their S,S^′-adducts were easier to reduce in the order of Ni adduct > Pd adduct > Pt adduct.     

Ferrous Iron and Sulfur Oxidation and Ferric Iron Reduction Activities of Thiobacillus ferrooxidans Are Affected by Growth on Ferrous Iron, Sulfur, or a Sulfide Ore

Eight strains of Thiobacillus ferrooxidans (laboratory strains Tf-1 [= ATCC 13661] and Tf-2 [= ATCC 19859] and mine isolates SM-1, SM-2, SM-3, SM-4, SM-5, and SM-8) and three strains of Thiobacillus thiooxidans (laboratory strain Tt [= ATCC 8085] and mine isolates SM-6 and SM-7) were grown on ferrous iron (Fe²⁺), elemental sulfur (S⁰), or sulfide ore (Fe, Cu, and Zn). The cells were studied for their aerobic Fe²⁺ - and S⁰-oxidizing activities (O₂ consumption) and anaerobic S⁰-oxidizing activity with ferric iron (Fe³⁺) (Fe²⁺ formation). Fe²⁺-grown T. ferrooxidans cells oxidized S⁰ aerobically at a rate of 2 to 4% of the Fe²⁺ oxidation rate. The rate of anaerobic S⁰ oxidation with Fe³⁺ was equal to the aerobic oxidation rate in SM-1, SM-3, SM-4, and SM-5, but was only one-half or less that in Tf-1, Tf-2, SM-2, and SM-8. Transition from growth on Fe²⁺ to that on S⁰ produced cells with relatively undiminished Fe²⁺ oxidation activities and increased S⁰ oxidation (both aerobic and anaerobic) activities in Tf-2, SM-4, and SM-5, whereas it produced cells with dramatically reduced Fe²⁺ oxidation and anaerobic S⁰ oxidation activities in Tf-1, SM-1, SM-2, SM-3, and SM-8. Growth on ore 1 of metal-leaching Fe²⁺-grown strains and on ore 2 of all Fe²⁺-grown strains resulted in very high yields of cells with high Fe²⁺ and S⁰ oxidation (both aerobic and anaerobic) activities with similar ratios of various activities. Sulfur-grown Tf-2, SM-1, SM-4, SM-6, SM-7, and SM-8 cultures leached metals from ore 3, and Tf-2 and SM-4 cells recovered showed activity ratios similar to those of other ore-grown cells. It is concluded that all the T. ferrooxidans strains studied have the ability to produce cells with Fe²⁺ and S⁰ oxidation and Fe³⁺ reduction activities, but their levels are influenced by growth substrates and strain differences.